A novel capillary fabricated by laser ablation was developed and applied to Hadamard transform capillary electrophoresis and post-column reaction for fluorescence detection in capillary electrophoresis. A small hole was fabricated at the center of the capillary. The small hole functions as an inlet port for the sample and labeling reagent in multiple sample injection and post-labeling reaction, respectively. In multiple sample injection, the hole is immersed in a sample solution and the end of the capillary that is usually employed for sample introduction is immersed in a buffer solution. A high potential is continuously applied between the injection port and the end of the capillary, which allows the sample solution to be introduced into the separation capillary. By application of a higher potential modulated according to a Hadamard code between both ends of the capillary, the buffer solution is injected into the separation capillary. This method was successfully employed for multiple sample injection in Hadamard transform capillary electrophoresis equipped with an absorbance detector and a laser-induced fluorescence detector. In post-column reaction, the hole was made at upstream of a fluorescence detector. The hole is immersed in a labeling reagent solution. Analyte zones separated by capillary electrophoresis were mixed with the labeling reagent introduced from the hole, followed by the reaction of the labeling reagent with analytes and fluorescence detection of the labeled analytes.